Process for the manufacture of esters



All@ 29, 1933- s. R. MERLEY Er A1.

PROCESS FQR THE MANUFACTURE OF ESTERS Filed June ll, 1928 Patented 29,1933` e commercial scale. l ,A furtherobjectof lthe,inyenton Vis thefp'ror duction of vtertiary" esters,th`at isjes'terscorresponding tothe tertiary fole'fin's present in the e `lfnooltss 'Fon 1,924,615 fTHEQMANUFACTURE F Y E srERsn `Sylvan RtfMerley,V Dover, N1 J., .and Otto Spring, i Okmulgee, Okla., assgnors ytofDohertyRc 'f search Company; NewYork, N. Y., a corporation of Delaware Application June 11, 19

2s. serialNo. 284,347.'

This'invention relates toa processy ofwandazpparatus forl the manufacture of organic esters.

More; particularly the 'invention relates tolthe` nianufacture of )esters from,l the unsaturated '5 hydrocarbons produced bythe cracking andre- `iningoi petroleum and natural gas. In therefining of *i petroleum, considerable quar'itities'` vof wasteY products,` particularly gases, are formedv 1 `Which containrolenic hydrocarbons suitable for l use Vin the presentprocess'.A Furthermorefthe oc'- sulphuric acid. ,This is particularly truevin the e' treatment of gasoline;

Processes are now known `and being' operatedin which alcohols are produced from olen hydrocarbons by the absorption of olefins withsulphuricl acid. lllsters `may be Yformedfrorn these anorganic acid in the` presence OffaQcatalyst alkyl sulphatea'obtained frompetro'leumby abture of the alkyl sulphates is dilutedk with Water and the 'resulting' mixture treated with `a lsalt of' an organicV `acid suchas calciumfeacetate.

While Ellis and Cohen suggest `,that organic n replacement of the sulphate radical `by'th'e ore ganic acid radical of theca'lciuin aeetateit' seems -reasonable to suppose that the'alcoh'ol isrst,

40 formed frornthe dilution with Water after which as inthe irst example referred. to above.

organic esters maybe eilicientlyproducedfon, a

Y oil products treated.

'In accordance with thisfobject, the processof the-.present inventionV comprises thejtreatr'rientY Y 559i alkyl sulphate liquor in Vsuch fa yvayals;` to ob-AA I tain yields of tertiary esterswhich willjvvarrantVV e l, drawing in Which` phuric acid 'to form alkyl sulphates and thes'ub-` sequent hydrolysis of these sulphates ,with yvater to form. alcoholsy and regenerate vthe "su1,

' or` otherlalcohols by treatmentof the same `with sorption with sulphuric `acid; in whichfa, rmix-A e e vtower ylbya valved pipe 8. esters are formedin this mixtu'reby the dire'ct esters are formed by interaction withlacetioracid `their manufactureon a commercial scalejv j previous vprocesses where, for example, it was desired vto produce 'tertiary hbutyl acetate from tertiarylbutylfaicohol and vacetic and, anche? l' j presence of a catalyst suchas. sulphuric acid, it has beerround that a yield. of approximately 6%esterisall that could be obtained. e, Furthermore,"` infattempts to prepare the estersof 4higher alccriols equilibrium was established with: ',amuclilower percentage of,.e`ster present; In

the*` case 'of the acetate offtertiary hep'tyl alcohol the manufacture'of:tertiaryesters. y

, Q With1theseand other objects in View `the rfeatures Vof the Vinvention) willnovv be describedin detail 'in connectione,with` the accompanying The figure is alowfshee't of ltheprocess'showingjdia'grammatically the apparatus adapted for v In` accordance ,Withjthe invention the 1olefin bearing material, which may be liquid'or gaseous;

or a mixturethereof, and derived from'anycon-f venientsource such asiromthe `cracking and/or' distillation of mineral oils n or"solid or ygaseous"-L 1 `hydrocarbon materialsgis introduced by a conduit 2 into" the` base' oi" an absorption tower 4 Where vit is, contacted with sulphuric acid in a counter'- ,i current `flow through the tower`- AThe;sulphuric acid maybe v` conveniently,taken ironia supply tank 6K and introduced intoftheupperyendof the The twer is preferably Aoff the bubblerpl'ate -90 @type .in Whichthej acid' acts `as the absorbing medium'to take up the `,olers fromfthe:l crude material.A Theto'wer is; also preferably provided i' ture may be held-at the desiredminimum"(niixuis4I 5? F) VAs theacid advances'downwardthrough the .tower it vbecomes; morer and more saturated fsothat` b'yfthe time it .reachesthe base" oflg'the 'columnit is comprised 'chi'eily pf mono- 'anddi alkyl sulphatesf;v

floofj e In the treatmengof nquirdoien bearing ina-f1 terialsfV such `jas., 'lovvfend-pbint .gasolineg-1 and still 1 Y Y vgasesorfa I nixtureofY gaslwitlh gasoline, thegaso'-Y i f line or" a gas-'gasoline mixture passesjupward;v

nn content is discharged from the separator by ra pipe 16.

During the ordinary operation of the tower the saturated acid liquor is drawn off from the base of the tower by a Valved pipe 18,*and collected in a settling'tank 20. Considerable trouble has been encountered when 66 B. acid has been used to treat liquid materials of the type referred to, be-` cause of the formation of a stable 'emulsion between the'acid liquor andthe gasoline so that the acid liquor and the gasolineV could not be Vseparately Withdrawn from the tower. It was discovered,y howeventhat this'conditioncould be corrected by using 85% acid atv temperatures Y suchthat the acid liquor .wouldV not freeze, or by bubbling a `gas through'the liquid on the trays in theV tower. This gas preferably' should be cracking still gas or vother gas'rcontaining olefins of low molecular weight and may be introduced through the pipe 2.

an volefin containing'gas for thepurpose of breakling'the emulsion in the tower A.or for the purpose of agitation when 235%Y acidislused itrnaybeA vented through a valved vent on the pipe 10.

, While the olefin content of va low boiling point gasoline may 'be effectively absorbed with sulphuricacid in the tower 4 without the addition thereto of gas, it has been Afound that the use of `gas is. very advantageous for commercial *opera--v tion. By controlling the acid strengthl and temperatur'es a gas which is substantially freeof olens may be effectively used in the towers for assisting in the absorption or conversion of the olefinl content of the gasoline into alkyl sulfat'es,

`and for effecting separation of the unabsorbed gasoline from the alkyl sulphuric acids. The mosteiective 'methodqvof carrying out the absorption,howeverf, iste'V use a gas containing oleiin, o particularly olefin of lower boiling point in admixture with the gasoline'to assist inpromoting the' reaction and in effecting v,the separation-` of the gasoline from the alkylsulphuric acid. fThe gas containing olen such Yas a cracking` gas or refinery gas gives 'an acid menstruum or alkyl sulphate wherein the alkyl compound is lower '.boiling .point hydrocarbon, and this menstruum f assists in promoting the reaction to help absorb the olefin content of the gasoline.

' v'The absorption in thetower may advantageously be carried out under a superatmosphericV pressure of from .30 to.15.0 pounds persquare inch, in which Vcase an equalizingV pressure line 22vis placed between the supplyr tank .6.r and the separator 12, or the YtowerY 4.`

The settling tank is made use vof'for theY fpurpose of separatingany gasoline or polymerized hydrocarbon which may' havebeen occluded in 4the saturatedv acid liquor. .These separated ma' terials-may be' decanted off byy a'pipe 24. The

` saturated acid liquor is comprised of monoand Adi-alkyl sulfates'corresponding to the olens of Amorethan two carbon atoms, present in the gas Vor liquid treated. The acid liquor mayalso contain' .some sulfates of cyclic oleflns and' also a;

.l small amount of-'freesulfuri'c acid. i

Y FromY the 4.tank "20 vsuitable quantities ofthe Where gas is used either tas' Y.Aside'rfrom these main'products, small amounts of low boiling ethers, ketones Yand jother com-A Y l l By the use ofr the gas an acid mixture of better consistency and higher concentration may be effected.

vided with mixing blades adapted for `the thor-` ough mixing of viscous materials.

Assuming thatmixer No. 1 is charged with the saturated alkyl sulfate liquor, a quantity of hydrocarbon `oil suchas' kerosene orother higher Y boiling cil',V equal to about 1sth the volume of alkyl sulfatesl is added from -a storage 36 by means of suitable valved piping 38, which alsor connectes with the mixerNo. 2. TheV agitation vor mixing ofthe liquor and the oil is now commenced-and at vthe same time dry commercialv yca'lcium'acetate is-slowly added from a storage v40 and conduit 42, and the contents of `the mixer `may be brought Ato' atemperature not to exceedl about F. 'The agitation during the addition vof the calcium acetate is preferably such as to leave a layer of oil lover the surface of the acid liquor so that nely powdered vvacetate may be added through the oil and thereby become coated with oil before it actually comes' into contact with the liquor. This method of. agitation and addition of the acetate will avoid to a large extent any Y undesirable reactions with the free sulfuric acid, and thus avoid local* overheating. Ifdesired the salt of the organic acid maybe previously mixed, with the oil and'` both introducedtogether into the/reaction chamber.

The quantity vof acetate Y added .shouldr be equivalent toV approximately 80% of the V.free and combined sulfate lor sulfuric acid inthe mixture and should be thorough- `iy incorporated thereinV Without' permitting any 5` substantial rise in the temperature ofthe batch.

'After the materials are thoroughly mixed fthe temperature of the' mixture is gradually raised over a period of fromthirty minutes to one hour.v

to a point netto exceed about 195 F.. at which temperatureY the reaction between the alkyl sulfates and calcium acetate will complete itself to producev organic esters and solid calcium sulfate.

pounds will `be formed as well as the liberation of acetic acid from any excess of calciumr acee 'tate present. In order to neutralize thebulk vof this excess organic acid, dry alcohols from a storage 44 may be 'introduced into the reaction mixture through the conduits 38 while there action temperature and mixing is continued.

The use of hydrocarbon oil in the esterication "of alkyl sulfates plays an important part in the process. Preferably, the'foil is added to the alkylA sulfate and the calcium acetate is added directly to the surface of the oil. The oil iioatingv on the surface of vthe alkyl sulfate, tends to coat the particlesof calcium acetate as it comes into the 'reaction and acts' as a stabilizer for controlling and promoting the' reaction. It has been found that the time required" for completing the re.-

action 'caribe verygreatly decreased-by the use j of thejoil controlling*r menstruum. AThis isdue to thefact thatif oil isnot used, a localized heating is caused bythe reaction between the alkyl sulfates and the'r calcium acetate whereby the oleiincontent ofthe alkyl sulfate is polymerized, some ofthe volefins arevolatilized and gases arev formedrwhich lentail vlosses and Yin order to` avoid these losses the calcium'acetate'has Yto be added g veryfslowlyto the alkyl sulfate solution jif noVv oilis used.r During the reaction between the calcium acetate and the alkyl sulfate solution alkyl acetates are formed and ltheseacvetates 'are dise, Vsolved in the oil. `This solution of eiland 'acetate protectsY thefacetate from the freel sulfuric acid inthe solution and thus prevents the'poly-- merizationy and decomposition of the-acetate be` lhigh volatile acetates are practically avoided In ing` formed. Furthermore, the oil vgives fa liquid menstruum in the reactionl chamber which aids in the separation ofthe calcium sulfate Vand the acetates. Alsobyhaving the alkylacetates dissolved in the oil the'evaporationflosses of the the esteiication mixers the use ofo'ilallows the 'products cannot beV properly,"` controlled. f e A further advantage resulting fromthe use of oil in the reaction mixers'-and stills is dueto the be readily separated from the acetate in solution. It has been found that ifno oil is Vused the calcium sulfate tends to set and give a stiff, muddy mixture of calciumacetate, alkyl sulfate andcal cium sulfate lso that the reaction between the fact that thev oil coat'sthe acid particles and walls of the apparatusand thereby protectsthesarne from'corrosion. The metal of which the apparatus is preferably made is more readily wetted byloilthan acid l The neutralization of theexcessorganic' acid f present `in the reaction mixturemay -be carried 4out in a separatechamber by decanting oif the ester and oil layer fromv the reaction mixturel and` fneutralizingthe same 'eitherwith dry alcohols or with lime;I Ii' desired .the excess organic acid may be'directly neutralized by-introducing lime into` -the reaction'mixer and steam dstillingf'of the esters which 'were formed Vin the esterication re- 40.

action. This procedure, however, causes the loss `of the excessv organic acid and also results in a `lower yield Vof esters. l the addition of dry alcohols to theesterification mass in order to take `advantage ofthe dehydrat; fing valuefof the calcium sulfate and sulfuric acid for the esteriflcation or neutralization reaction` The preferred method is `betweenthe added alcohols and acetic acidpres- .ent inthe mixture. Y Y been found that the waterformedfin thiskstep, Vof the process causes the settingor'granulation In 4this connection, o it has of the calcium sulfate and thereby-facilitates its precipitation in the mixture. While it is preferred to neutralize part' of the vexcess organic acid while theesters are in the mixer, it has been found inadvisable to complete the neutralization therein because of theilfree sulfuric acid present,

since vany rise in temperature'would cause A4decomposition'of the:` tertiary esters and part of the secondary esters. Y o l I,

IThe light ethers, esters, ketones-and 'other' compounds as wellas partfof thealcohol added may be volatile` at the temperatures employed so inY order to prevent their-loss from the'systemfthe* 'esterificationmixers are provided witha refluxing system whichV comprises vapor.v lines 46, con-r ydensing' coils A48 mountedl in a'coolerj50," condensate traps 52, condensate V"return .lines 54 andY therefore scrublced'inl a scrubber'58 with an alka-b --line solution to remove the 'SOzafter whichfth remaining vaporsvmay'be recovered byrefrigerai gas or uncondensed .vapor vvconduits 56 which lead throughjethe cooler 50.I 'Thefgaslcondueted f away'by the. lines 56 contains S03v `andvery light ethers, ketones and aldehydes, This gasis jln order A'to make`fthefprocess-y continuous two reactionmixers 5 are Iusedv so that while one is itseontents are again cooled down to normal and "being elrlptied-an'd cleanedthe other may beset .i'n operation.` After thecompletion'of-there- *action and; partial' neutralization inj-"either mixer 8O then the ester or oily layer isf decanted off and 7 vthe calcium sulphatejresidue Washed'withoil to "removeoccluded estersftlieester layer and washingsA being *conducted by `valved pipes-60 and pump 62 to one of two settling tanks 64'. v"Theoily y layerand washings taken from the mixers 32 `comprises vr'the hydrocarbon oil-v added, the. esters v'formed'a'cetic acid, alcohols and Small vamounts ofv impurities such as polymers, and occluded calium. sulphate. The VSettlingtanks s4 Ypermit the separation of any?V sludge acid or re'sidualfr'naf lserial from the ester-oil mixture by, meansof valved drain pipes 66.Av

2.95', VThe Vresidue remaining rinthe mixersu after the removal of the mixed estersand oil'eonsistsmainl the mixture inthetanks 64 is treatedin' the following manner: A; batch of mixedyes'ters-is drawn l from either of the tanks 64 by means ltifsuitable valved piping 'IZ-andpass'edt eitherone of two neutralizing stillsi74'which may be vrun i in succes- `sion 4in order to makef the processfcolfinuous. Each of th'ese `stillsis cnstructedalike and may be heated in anysuitablemanner, eachstillisalso provided with a reflux column 76. The batch of esters and oil inthe neutralizingstill is heated -to produce vaporization. TAs the vapors pass upward through thecolumn 76 kdryalcohol or alcohols are introduced intothe upper" portion' of thej column as bymeans of a valved vconduit `78,or``

the alcohol may be introducedA into the still 74.

The alcohol serves to neutralize any acetic `acid Y' which maybe present in the mixture; During the reuxing and neutralizing foperation 4vapors are conductedfrom 'thefcolumn by means of a valved vapor -lie 80 and `condensedin ja condenser- 82, l

thel'condensate falling backv into ai trap 84`where 'l thewater lisrexnoved by Va pipe 8 6 andtheester, oil-f and alcohol `layer returned to the stillf '14by meansrof a liquid sealedreturn line 83.

The waterremoved by the traps84 is `the Waterof reaction producedin o the' neutralization of the aceticlacid by the alcohol. After thea'cetic acid A `inthe-ester mixture hasV been completely neu- 1.30 `V`tralized ther introduction ,of alcohol is" discon-v tinued and thevapor streamis the'ndive'rt'ed from -the condenser 82 through a'vapor'lineSQ into the mid-portion of a 'rectifyingcolumn 92.

The aicohoi introduced into me columnas' '16 may be introduced in small quantities as the neutralizationrproceeds o`r the l'whole 'amountfoalv 'culated to be .necessary may be introduced into thestills v'74 before the distillation is`co1'r`1`menced. 'rhe'column aztogether `with' a stiu 94, acon-j J-}denser96 jand a separator trap 98' isoperated'esf lsentially as aV steam distillingunit, v The' 'vapors ``introduced intoN thegmid'portion' fofthefcolumn f nf92are:comprised ofmixed esters and. light ,frac-4 mixers 32 when the foil used A.in the `mixers` isl a relatively low boilingpoint oilgsuh as,v light'akroi t e seme, ybut the greaerrportionofithe hydrocarbon A constituents carriedby these l'vapors' 4arie*c lerivedl `fromthe 'hydrocarbon polymer material dissolved A in the saturatedfacid withdrawnfrom the-absorpy tion tow er 4.. .These vapors immediately come into Contact withwaterpassing down thecolumn `or withi-steam vpassing up. The water serves to fc-ool the ester-oilvapor and condense the oilwhile the' esters steam distil over into thecondenserf,

where they are condensed and collected in the'sep- {sealed return line 104.

varator 98. .The esters are insoluble'in the water .a specicexample. An isopropylv acetate fraction with light hydrocarbons from oneof the columns '76 will-enter lthe rectifying column 92atfa .tem-

L perature of` about 89". C., but isopropyl acetate-dis'- '-s tills' with water at 76.4"v C., therefore'the temperature of the entering vapors mayfbe lowered about 12 C. and s tillbe high enough to steam dis- .till the ester; yat the: sametime this lowering temvperature serves to condense the oil-vapors. .This

' cooling therefore isfconvenientlyeffected by the ythe column 92,"or other-points in the column. For

introduction of water into theupper portion of example,y the Water-from the traps 84 ispreferably for a new batch of esters. f

introduced into the column 92 bythe pipes 86 vso that any esters which may b e present therein may berecovered.

The stills 74 are preferably` operated alternately in such a manner that the columnV 92 may be opolens of the same character Yas thefacetates rare derived from. Generally the acetates inthe mixer 32 and still 74' are mixtures of racetates comprising principally isopropyl acetate, seconderated continuously..A Whenthe esters in either of the stills '74 have been completely driven over into the column 92 the remaining oil isdrained therefrom by means of a valVed-cleanout pipe 106,- into an oil storage tank 108. The -still is then ready AThe still 94Vserves mainly f'orsupplying heat and steam for the column 92 and as acollection u vessel for oil and water, the former being decanted by means of a valved pipe 110into' a separator 112 where the oil and any water present therein maylbe separated. The separated Ioil is sentto f `:the storage 108t vThestill, 94 is also provided with' .a. valved cleanoutdrain 114, whichmay be used t-o drawof the water layer from-the still. 1

y Certain elements of the apparatus such asthe reaction mixers 32, the tanks 64 and the stills 74, y together with their' related equipment, have beenV4 shown in ,duplicate for the purpose of illustrating the process as operated continuously. It is .to` be understoodthat it maybe operated'with but a single reaction chamber32 or still 74, or Ywithmore 1 than two of these units in vorder -toproperlyeconomize the manufacture and utilize the capacity of the tower 4 and purifying column'f92.:

OneY of the important features of the present in- Vention is the production of .tertiary esterscorrespending vto the tertiary olens present in cracked petroleum products. 'It is highly important there- Y fore that the absorption in the tower 4.be carried f Yout under-such conditions as to-cause aminimum of polymerizationof the olens. For example; Vthe temperatureat the baseof the tower where the'.

oleins rst contact the acidliquorshould bein the neighborhood 4of about 5 F., While thetemavailable propionate. gasoline or kerosene containing particular olens' such as to favor Atheabsorption of thetertiary olens without substantialA decomposition. Itis generally V.recognized that ltertiary organic compounds are V much more unstable and more difcult to, p1 ep are than the primary and secondary. In fact the experiments conducted in connection -with-.this process show that even though the tertiary yolefins. may be converted to the tertiary sulphates by carefully controlling the absorptionin the towe r "f1 ,;only minute quantities of tertiary orgarlic esters; willbe formed if the ,acid.liquor is dilutedgwith water before addition of the esterifyingf agent, such as calcium acetate. It is therefore very important that the esterication reactionbe 'carriedout under substantially anhydrous conditions in order to obtain the tertiary esters, .or

lto `obtain a payingyield of any esters. Under all circumstances'the esterication should be conducted under such conditions thatthe concentration of'sulphuric acidis such as to haveagreater aiiinity for any lwater ofA dilution in theoriginal acidforacid liquor, or for any moisture present in the dryfcommercial calcium acetate, than the alkyl radical would in order to be converted.` (hydrolyzed) to the alcohol. Andyet the acidmust. not bepresent in such a concentrationv or ary butyl acetate, secondary amyl acetate, secondary hexyl acetate and secondaryheptyl acetate. Furthermore, `the mixture'may also contain the secondary octyl, nonyl and decyl acetates as well as tertiary butyl andv amyl acetates. Preferably therefore the alcohols would be the corresponding secondary and Ytertiary alcohols derived from the secondary and tertiary olens.

It has been found however that the alcohols havingftheihigherfboiling points, that is,the

alcohols higher than butyl may be acetied much more readily .thanthe lower alcohols. Therefore the time requiredffor neutralization of fthe excess acetic- Vacid may fbe materially reduced by using the, higher boilingg-point alcohols. ."Thus if it is desired to' produce' the .esters derived from higher boiling alcohols'thehigher alcohols may be used for'thezneutraliz'ing operation; In thecomrnercial processy two forms, of rdry alcohol are. em-

ployed for neutralizing, one-alcohol is'a so-called low boiling alcohol-comprising principally isopropyl valcoholand somesecondary butyl. VThe .other alcohol is` Aa mixture of the alcohols higher inthe lolen, series than propylenefi. e., secondr ',ary'butyl, amyl', hexyl andthe higher alcohols.

While in describingthe process ofthe invention specific mentionhas been made of the treatment of mixtures of yolefins present in various petroleum products and the production of mixed .esters therefromzit is. to1be understood that the .Y at. sucha temperature or both aste'` convert the Yalkyl sulphates into polymer bodies or other deneY lio,

Y ,considerable aflinity for the inorganic acidvradif. cal, although. this factor, is not asv importantas boiling in a definite temperature range may be treated by the same process; i g

The formation of the 'organic esters-,in the process described above by the directreplacement ofthe inorganic acid radical bylan` organic acid radicalis apparently accelerated .by the use of a salt of the organic` acid kwhich will have itl would be `the reaction could `be carried out in the Apresence of water. `of the desired organicacid maybeused.V

. Organic esters maybe conveniently made with other startingmaterials particularlyif these ma- 51:5

terials happen'to` be inexpensive at the place of manufacture. For examplegra :halogen'acid such as hydrobromic or hydroiodic may beused `to react with vthe olen to'yiel'd the alkyl ester (or halide) after which `the halogen' may bevreplaced by 'any desired organic acidfradical from a suitable salt. The treatment of analkyl chloride with a calcium salt of an' organic acid gives ybesides the organic ester, calcium .chloride which action during the addition 'ofi-the esterifying salt. A'

' Having described the invention in its preferred 'form what is claimed as n'eW'is:

" carryingt'outthe reaction betweentthe inorganic would prevent thehydrolysis of the ester duringitsV formation and Vinsure its dryness for subsequent distillation.` In such reactions it `is pre-` ferred to have a small amount of inorganicacid present .in` the' mixture; The. invention is not limited to any particular method of makingthe alkyl ester of the inorganic acid, such as alkyl `chloride vsince kthese compounds may be .made 'frm saturated hydrocarbons'by direct chlorination. f Furthermore, the alkyl di-halogen compounds may be'esteried in thejsame manner as the mono-derivatives, to give either the halogen organic esters-or the] alkyl di-esters fsuch vwas isobutylenepropionate Vor other `alkyl di-l .propionates or esters of similar structure.

In the use of a hydrocarbon oil in the esteri-V Ification step, the oil, vwhich may begas oil 'or other oilnot havingtoo high av viscosity, is not t' agitated with-the acid liquorto such an extent as'to c ausecomplete emulsication. Themai purposes of the oil is to increase the fluidity -v of the mixture and `to'aid in' tempering there- 1. In the process voff,man'utacturingt'tertiary alkyl organic esters from a tertiary alkyl sulphate containing product, byireactigtherewith an in- 4 `organic salt of an organicV carboxylic acid; the :improvementwhich `comprises mixing a substantial 'quantity of sati'iratedl liquid hydrocarbons organic acid, Vvthe` improvement lwhich comprises ester and the salt of theicarboxylic acid under substantially anhydrous, conditions, separating i 5 esters `corresponding tertertiary-alcolrilsbyj're- Athe resulting tertiaryA organic ester fromfthe reaction mixture, adding a quantity of Idry alcohol "to neutralize 'any excess organic acid 'present in the resulting ester'product, and steam ldistilling y*themixture to recover the tertiaryorganic'ester. y 3f: In "theV process "of manufacturing,` organic Any availablesalt Y separating-the tertiary organic esters from'the- Vcondensation vin thelpr'esence ofV dry alcohol; 1

esters byreacting;

" agitating -the Vvresulting mixture slowly adding" -tion occurs, thereafter raising thetemperature to a point notfexceeding approximately .'l95?f-F. f whereby 'saidreaction is consummated, and sepa- .ganicr acid formed 'during the reaction. y

acting 'tertiary alkyl sulfatesjwith an inorganic salt of .a carboxylic organic, acid,V the improvement .which comprises; mixing i a hydrocarbon .oil with afquantityof tertiaryalkyl sulphates,

agitatingfj the resulting mixture and slowly v,adding the csaltof thelorganic acidfin a lquantity, equivalent: to substantially ofthe sulphate ,presentinthev mixture, thereafter increasing the temperature of the resultingmixturefto a point not exceeding195 F. whereby thes'ulphate'radical is replaced' by the vorganic acidfradicaL fadding a quantity ofdryalcohol'to the mixture to partially neutralize `excess-organi'c acid evolved,v

reaction 'mixture'and subjecting themto reflux 4.",In theLprocess :of manufacturing tertiary I -alkyl organic esters:from"a mixture" of tertiary alkyl sulphates byjreactinglvtherewith a`n` inorl ganic` salt of an organicscarboxylic, acidftheimprovernentI which comprises adding 'to themix'- V,ture of tertiary alkyl sulphates Vs'ubstantially one n 'K fifthV its volume of hydrocarbon oil` fand while simultaneously, agitating`-ar1d` cooling theflres ulting mixture adding-thevsraidf-salt `tobere- 100,y vacted with the" alkyl fsulph'ate's, separating 'the resultingv organic. esters formedI ir-i; the reaction mixture, vapori'zin'g thefseparatedesters andintroducing theyapos intoa column still inv coni' tact'with 5. In fthe" process .of fmanufacturing tertiary; alkyl' organic'f'estersin which tertiaryV alkyl sulphatesare reactedwith an#` inorganic salt'o'f'fa'r'i organic carboxylic acid, the improvement whi'ch 110' 'comprises "carrying o ut the-reaction under sub-` stantially anhydrous conditions, maintaining-the temperature during" vthe, mixing `Aciffsaid constituents approximately '70"` F., thereafter.y raising fthe temperaturelto' apoiiit not'to'jexceed 1957F, Y'115 'whereby the reaction betweenfsa dl'eonstituents is completed., and separatingv the resultingesters :mixture of'- alkyl testers; fof an inorganic acid ,withaaninorganic salt-of anV organic carboxylic acidf the improvement which ganic acid with la hydrocarbon oil, and" their;vvliil'ev the inorganice salt o'f the organicgacid, maintainfing the"-temperature ofthe mixture while adding said salt'below'thatfat which a substantial reac.- l

-frating'thejresulting V"alkylY organic esters. I

t f7. I n the process tot 'manufacturingjalkyorganic 'esters byreacting a'fmixture of alkylfesters? l f of an inorganic acidwlth ar'i'inorg'anic salt-of an organic carboxylic acid, the improvement jwhich Acomprises adding the salt in sufiicient' `quantity to the alkyl esters of the inorganicacid to'rr'eact with substantially all of theA alkylvzbodies present -"therein, carrying out therea'ction under substa-''MO tially "anhydrous conditions,l and adding 'toV 'the' resulting'mixturea quantityjof dry; alcoholl suflicient* to ,substantially neutralizethe" excess or-l' 8.' In the "process of t. Ar'na'xfiufa@ :tuiing 1 organic .5 esters "by reacting i aj quantity-fof falkyl sulphates "with an inorganic saltof` an `organic carboxylic `vlacid, thev improvement which `comprises adding Y p, fo che quantity. Ofrsulphaws Subs/wn'tia411s"V miie-@H lfthfitsvolume of hydrocarbon'oiLadding to thel 150 water therebyvsteam distiuing the esters r-frorn v impuritiescontained therein".v j

-organjic y 'Withthe organic acid radicalin saidsalt-.and add-L ing a quantity of dry alcohols to said mixture to neutralize'substantally all of any excess* organic Vacidgiormed by said reaction.

9;. In the process of manufacturing' alkylor-v ganic esters ,by reacting alkyl'sulphates WithanYV inorganic 'salti of .an organic. carboxylicacid, the

, improvement which.comprises first adding a sub- A .'stantial quantitygof hydrocarbon oil toa batchV .of said sulphates, agitating and cooling the resulting mixture and then addingsaid salt .While lcontin'uingI the agitation, and thereafterraisingthe temperature .ofl the resulting mixture.,whereby alkyl organic esters are formed therein. I 10.r In the process of manufacturing alkyl organic esters from alkyl vinorganicesters by re- Y acting 'therewith an inorganicsalt of an organicY carboxylic acid, theimpr'ovement With comprises mixing, al hydrocarbon oil with a batchrof alkyl ganic esters from alkylsuliatesby reactingrthereinorganic esters,i agitating therresulting mixture, and simultaneously `adding .thereto the inorganic salt, of tinorganic acid bringing the resultingy mixture to a temperature adapted-to furtherv the said ,salti thereby tok produce the desired organic `alcohol whereby excess Vorganic neutralized. 1 l

acid jpresent is 11. In the vprocessiof;manuiacturing alkyl or- With anl inorganic saltfof anorganic carboxylic acid, the improvement Whichcomprises carry.-

ing'out the; reaction under'substantially anhydrous conditions, separatingthe organioesters tion, and steam distilling the separated esters.

. .12.- In the process ofV manufacturing` mixed 'alkylorganick esters Ifrom a mixture of alkyl sulphates by yreacting therewith an inorganic salt Q f an Organic carboxylicfacid, the irnlfircpvement which comprisesmaintaining the temperature Qduringithe mixing of said compoundslnot substantially above Fi, Vadding said .salt inra quantityequal Vto substantially80% of the sulp hate present in the mixture, and thereafter in- V'creasing .the temperature toa pointnot exceed-l `ving 19 5",A.F..,thereby forming, the desired ,alkyl organic esters.` Y 1 13. yIn theprocessof manufacturing analkyl organicfester from analkyl inorganic ester by ganic .carboxylic acid, the improvement which ncomprises mixing the'rsaid compoundsrundena 'temperature 'Substantia11y..'be1owthat at which lthe'esterii'lcation, reaction takes place, thereafter raising the temperature ofthe mixture to that at .whichthe desired reaction iscompleted, carrying (55.;V

out the reaction vjunder `substantially anhydrous conditions,v and separating the resuitinge'ster pro- ,Y ,ductr from the residual 'products of the reaction. 3, 14. In thejprocess of manufacturingy organic esters by the interactionof an alkyl sulphate and aninorganic salt of an organic carboxylic acid,

1f the improvement ,whicuh comprises kmixing the alkyl,sulphate;n a Ahydrocarbon oil `and j.the said salt in a reaction chamber, heating and agitating A themixture in saidrchamber tonefect a reaction between the alkyl sulphate andthe Vsaid Asalt s'aidreaction chamber and subjecting'thesame to .reux distillation inZ the presence. of additional v quantitiescofl said alcohol,f.condens ing the vapors producedin said refluxy distillation, separating the. Water :from the. condensate and returningr the remainder ofthel condensatefto the* reflux oper'ation, and thereafter separating the organiciester from vthe oilyv mixture bymfra'ctionaldistillation. 15. In the process of manufacturing organic esters from a mixture of alkyl sulphatesV by. re'- actingtherewithan inorganic saltaof an korganic carboxylic` acid, .the improvement which .comprisesintimately mixing saidsulphates with said salt in the presencetof a hydrocarbon .oil under substantially, anhydrous conditions`, heating said mixture to cause the direct formation ofV organicl f esters from said sulphates and saidsalt, adding a quantity ofmixed'alcohols corresponding ,to the alkyl .groups .in vsaid .alkyl`sulphates`, and continuing themixing ofthey materials until 'a substantial-'portion'.ofithe excess` organic acid lib-- erated .byi'the .reaction lhas been neutralized, 'drawing off into areflux still the oily layer com-- prising oil and. theA esters .produced-Washing rthe -residue in the reaction chamber'to remove additional quantities of` esters therefromV and adding it to the Withdrawn oily layer infsaid still, adding additional quantities ofesaid alcohols .to the material in saidstill, and subjectingthe mixture to reflux distillation'for a period of;r timesufcient' to completely neutralize any ,organic acid presentVV therein, .thereafterl vaporizing the esters in said Still'and'passing. them into .Contact :with water in a purifyingl tower thereby to cool saidvapors :and steam 'distill the esters.. f j formedfr'omfthe residuaLpi-oducts of the reac- 1.6.l In the process of manufacturing organic esters from a mixture of alkyl sulphates by reactl carbwnrlicA acid', the improvementxwhich r.com-

mixer, with va quantity of hydrocarbon voil Which forms a layer over said sulphates, slowly adding theinorganicsaltgthrough said layer of oil while `continuing 'said agitation, heating the combined 4mixture inthe reaction mixer yto effect the directl replacement of ,the Sulphate radical in said sulesters from saidreaction mixer and subjecting the l v n k,same y-tofreiluxfdistillationdn the presenceof c reacting lltherevvith an inorganic salt of, an oralcohol thereby toA neutralize any organic acid present in theesaid `'Withdrawn layer,A condensing ,the vapors produced in said 'reuxdistillatiom separating waterffrom the condensate andrerefluxing 'operationand thereafter removing the esters from said s tillbyfractional distillation. r

acid by y.reacting therewith an inorganic .salt of an/org'anic carboxylic acid, the :improvement ,l which comprises mixing .the alkyl esterof the inorganic acid, a hydrocarbon oil, an .inorganici acid,. andthe inorganic salt of an organic acid,

4phates by the .organic acidy radicalinsaid salt thereby to form a mixture of organic esters;v removing'nthe oily 'lay-,eli containingvthe organic '1,130

Iturning the remaindenof the condensate tothe said saltbeing added in. excess of the quantity necessarygtofreact with -thequantityof alkyl inorganic esterpresent inthe mixture for vthe pro- Vf i'uction of saidorganic ester, controlling thetem-i perature of the resulting mixtureto cause the direct formation of saidforganic ester and the liberation of excess organic acidfrom said salt, withdrawing the resulting organic ester and organic acid from the reactionmixture and neutralizing the organic acid with an alcohol.

' 18. In theprocessy of manufacturinggalkyl organic esters from` an alkyl ester of an inorganic acid by lreacting therewith an inorganic salt of a carboxylic organic acid, the improvement which comprises mixing the alkyl ester and the inorganic acid with a relatively high `polling point` hydrocarbon oil and the inorganic salt of the organic acid under controlled temperature `conditions in the presenceof `a small proportion of free inorganic acid, allowing thereactionbetween the alkyl ester of the inorganic acid and the salt to go to substantial completion, separating the resulting oily layer containing` organic ester and organic acid from the remainder of the reaction productsj dry distilling the organic ester` and organic acid from the oiland neutralizing the organic acid with alcohol in the presence of .the organic ester.

19. In theprocess of manufacturingalkyl 'or vganic esters from an alkylester of` an inorganicv acid by reacting therewith anV inorganic salt of an organic carboxylic acid, the improvement which'comprises mixing the alkyl ester of the inorganic acid with a relatively high boilingpcint 'laction of the mixed .materialsf separating the organic ester and organic acid from the oil, and

, neutralizing the organic acid"With'substantially dry alcohol in thepresenceof said'lorga'nic ester.

20. The processof manufacturing organic' esters, which comprises adding a 'hydrocarbontoil to a mixture of alkylesters of an inorganic acid, agitating the resulting mixture and slowly addinga-salt `of an aliphatic monocarboxylic acid while maintaining a temperature belowfthat at.

which a substantial reactionoccurs, thereafter raising vthe temperature to a point not exceeding approximately 195 F., whereby saidreaction` is consummated, and separating .theresulting alkyl organic esters formed. y

Y v ganic esters, which comprises 'treating amixture of alkyl esters of-'an inorganic acidundersubstantially anhydrous conditions Witha sufficient quantity of a salt of an aliphatic monocarboxylic acid to react with substantially all of the alkyl bodies present therein,l andadding `to the resulting mixture a quantity of drykalcoholsuic'ient to substantially neutralize. the excess of organic vacid formed during said reaction. Y V22. Theprocesswof manufacturing an alkyl or.- j ganic ester from an alkyl sulfate, which com-- prises-adding a substantial quantity of hydrocarbon'oil to `a batch of said sulfate,.agitating and coolingthe mixture, adding a salt of an `v aliphatic monocarboxylic acid to vsaid mixture 2l.. The process-"of manufacturing alkyl orduring said agitation, and thereafter increasing the temperature of said 'mixture whereby an alkyl organic ester is formed therein corresponding to" said acid;

t The process of manufacturing an alkyl es" ter of an organic acid from an .alkyl sulfate` un- 1 der substantially anhydrous conditions, which comprises replacing the sulfate radical Ofsaid jalkyl sulfate with an aliphatic monocarboxylic.,

acid radical by treating said sulfate under sub-l stantially anhydrous'conditions with a salt of an 1 aliphatic` monocarboxylic acid, separating thef,A f resultingorganic esterV formed from the residual Yproducts ofthe reaction and distilling the 'same`.

24. Theprocess ofrmanufa'cturing an' alkyl organic ester fromV an alkylinorganic ester, ,whichA comprises mixing van'alkyl inorganic ester under substantially anhydrous conditions, with a salt y' of an aliphatic Vmonocarboxylic acid while mainf taining a temperature substantially'lbelow that yat which the esterifying reaction takes placeand after the mixingof said compounds rai'sing'the l temperature ofthe mixture 4t0 `thatat Which-the 1l desired-reaction"takes-placeQwhereby the inorganic acid .radical'ris replaced by theialiphatic` `Inonocarboxylic acid radical, and separatingthe resulting ester'fproduct fromftheresidual products of the reaction. H

25. The processof manufacturing organic esters,which comprises introducing an alkyl .sul-

fate, a hydrocarbon oil and a' salt of an aliphatic c i monocarb'oxylic acid into av reaction chamber,

heating and agitating the vmixture in said cham-`v y ber to effect a reaction between the `alkyl'sulfate land the salt of the aliphatic monocarb'oxylic acid Y to producel an organic ester, introducing'an al-y 'coholcorresponding to the alkyl group of said alkyl sulfate .into said reaction mixture thereby vto neutralize a portion ofthe excess aliphatic monocarboxylic acid liberated from said salt,V [removing the oily layer comprising the oil and organic `ester .from said reactionI chamber and subjectingtthe same to reflux distillation' in'the presenceof additional quantities ofsaid alcohol,

condensing theyapors produced "in said reflux distillation, separating the Water from thevc'ondensate andv returning the ,remainder ofthe condensate to the `reiuxing'operation, and Vtheremixture by fractional distillation.

after separating the organic ester fromthe; oilyv 26. The process of manufacturing alkyl organic.` esters, which comprises mixingv a `quantityof an alkyl ester of an inorganic acid under` substantially anhydrous conditions'with a hydrocarbonV oil, inorganic acid and aV salt 'of an` aliphaticv monocarboxylic acid, said salt being'inf excess of) the 'quantity' necessary vtoreact Withsaid y quantity of alkyl inorganic ester ,for` the :production of said organic ester, controlling the tem- 7 perature ofthe resultingmixture to cause'the '35' rdirect formation of said organic `ester and the y liberation `of excess aliphatic monocarboxylic acid from said salt, withdrawing the'A resulting organic ester and aliphatic monocarboxylicacid from the reactionmixture, and neutralizing the aliphaticmonocarboxylic acid Withan` alcohols "-,sYLvAN R. MERLEY.' L

vo'rrol SPRING,VIV L 

